ES2612303T3 - Method and device for the continuous production of hydrogen sulfide - Google Patents

Abstract

Method for the continuous production of H2S hydrogen sulphide, where polysulfan (H2Sx) content is found in a flow of crude gas containing H2S that occurs during production, characterized in that the flow of crude gas is conducted at temperatures of 114 to 165º through catalytically active material (41) that is contained in a container (42), and the sulfur that accumulates in the bottom (43) of the container (42) is collected and redirected to produce H2S, where a refrigerant enters (40) and the reactor (1) is arranged a line (30), through which the flow of crude gas is conducted in a direction from the reactor (1) to the refrigerant (40) and is conducted in a opposite direction, from the refrigerant (40) to the reactor (1), through the redirected sulfur.

Description

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DESCRIPTION

Method and device for the continuous production of hydrogen sulfide

The present invention refers to a method and a device for the continuous production of H2S hydrogen sulfide, where in a flow of crude gas containing H2S that occurs during production are polysulfan contents (H2SX, where x> 2).

In the state of the art, the production of hydrogen sulfide takes place, for example, through the H2S method according to Girdler (Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2003, vol. 17, page 291). H2S is produced noncatalytically from the sulfur and hydrogen elements in a column with inlets and with an enlarged bottom, essentially horizontally oriented. In the bottom filled with boiling sulfur hydrogen is introduced, where the sulfur is carried by steam towards the ascending gas phase. Hydrogen and rising sulfur react in the gas space of the column, where the heat of the reaction that is released is extracted to the product gas through washing with liquid sulfur. To do this, from the bottom of the column liquid sulfur is extracted, mixed with fresh, fried sulfur, and placed on top of the column. The product gas that contains a large amount of hydrogen sulfide is cooled in two heat exchangers.

A catalytic production of H2S is described in Angew. Chem .; 74 year 1962; No. 4; page 151. In that case, the hydrogen is conducted through an externally regulated sulfur bath in terms of temperature. Hydrogen loaded with sulfur vapor enters the catalyst chamber through perforations. The sulfur that has not reacted, after leaving the catalyst chamber, condenses on an upper part of the H2S outlet tube, reaching the sulfur bath again by means of a return tube. The catalyst chamber is arranged concentrically around the H2S outlet tube.

From the application DE 1 113 446 the catalytic production of hydrogen sulfide is known through the conversion of a stoichiometric mixture of hydrogen and sulfur into a cobalt and molybdenum salt in a catalyst containing a support, at temperatures between 300 and 400 ° C The catalyst is arranged in tubes that are crossed by the mixture of hydrogen and sulfur. The sulfur bath has a temperature of 340 to 360 ° C, due to which a stoichiometric mixture of hydrogen and sulfur is generated through the passage of hydrogen through the sulfur bath, for the production of H2S. The heat of reaction that is released during the formation of H2S is used through direct heat exchange, since the tubes containing the catalyst are arranged in the sulfur bath, in a way that is not described in detail.

In US application 2,863,725 a method for the production of H2S in a molybdenum-containing catalyst is described, where gaseous hydrogen is introduced into a reactor containing a sulfur melt, ascending through the sulfur melt in the form of bubbles. Of gas. The amount of hydrogen introduced and the temperature of the sulfur melt, where a temperature below 326 ° C is indicated, are regulated so that a gas mixture that is formed above the sulfur melt in an area of Gas contains the hydrogen and sulfur educts with an excess of hydrogen above the stoichiometric reaction ratio.

During the synthesis of H2S from hydrogen and sulfur, polysulfanos (H2Sx) are usually found in the raw gas as secondary products. For example, in a gas cooler connected downstream of the reactor, at certain temperatures, up to 1000 ppm weight of disulfan H2S2 can be formed, as! as higher H2Sx sulphanes, which in subsequent stages decompose again forming H2S and sulfur, so that in the pipes, valves, compressors, heat exchangers, etc., unwanted sulfur precipitations can occur.

The application DE 102 45 164 A1 refers to a method for converting polysulfanes into H2S and sulfur, where the H2Sx polysulphanes that are contained in the raw gas streams containing H2S that occurs during H2S synthesis, are cataloged into H2S and sulfur. For this, the raw gas containing H2S, for example, is brought into contact with a suitable solid body, catalytically active, in particular with active carbon, Al2O3, SiO2, etc.

Application FR 28 44 208 B1 refers to a method for purifying a synthesis gas containing mainly hydrogen sulfide, obtained through the reaction of hydrogen and liquid sulfur in a technical device, where said gas is conducted through a filter containing a solid substance selected from porous particles of active carbon, aluminum oxide and silicon oxide. The filter material (for example active carbon) is consumed after being loaded with sulfur and, by way of example, must be removed through combustion. The high maintenance investment for the change of the active carbon bed, the continuous consumption of active carbon, the disposal costs and the environmental damage produced during the combustion of carbon are considered as disadvantages. During the period that requires the change of active carbon, at least one other active carbon station must be transferred.

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Application US 5,686,056 refers to a method for purifying hydrogen sulfide gas with impurities containing polysulfan. The method comprises guiding the hydrogen sulfide gas through a filtration medium comprising a molecular sieve, where the polysulphanes are broken down into hydrogen sulfide and sulfur, and the sulfur that is presented is maintained in the filtration medium. To separate the accumulated sulfur from the filtering medium, heated hydrogen gas is conducted in the opposite direction (as compared to the hydrogen sulfide gas direction) through the filtering medium.

In Ullmann's Enzyklopadie der technischen Chemie, of the Chemie publishing house, Weinheim, 4th edition, volume 21, page 171, it is described the fact that hydrogen sulfide leaving the reactor on the top, after crossing a direct exchanger with approximately 200 ° C, is conducted through a coke filter, in which sulfur that is entrained is separated.

According to the application DE 558 432 hydrogen sulfide is produced by conducting hydrogen over a liquid sulfur sprinkler. The gases generated pass through a catalyst and, for the separation of the sulfur that has remained in the gas, they are conducted from the rector to a refrigerant. From the refrigerant, the sulfur is driven back to the bottom of the reactor.

The object of the present invention is to provide a method and a device for producing hydrogen sulfide, which avoid the disadvantages of the state of the art. In particular, it is the object of the present invention to provide a method and a device that enable the production of hydrogen sulfide as pure as possible, with sulfur proportions in the gas that cause the least amount of precipitation possible, with the lowest possible cost.

According to the invention, said object will be achieved through a method for the continuous production of H2S hydrogen sulfide, where in a flow of crude gas containing H2S that occurs during production, polysulfan (H2Sx) contents are found, where The flow of crude gas is conducted at temperatures of 114 to 165 ° through catalytically active material that is contained in a container, especially preferably in the active carbon that is contained in the container and / or in the molecular sieve. that is contained in the container, where the sulfur that accumulates at the bottom of the container is collected and is redirected to produce H2S, where a line is arranged between a refrigerant and the reactor, through which the gas flow Crude is conducted in one direction from the reactor to the refrigerant and is conducted in an opposite direction, from the refrigerant to the reactor, through the sulfur reconduc gone.

The flow of crude gas containing H2S can be produced according to one of the methods known to the expert, for example according to Ullmann's Encyclopedia of industrial Chemistry, sixth edition, of the Wiley-VCH Verlag (2003) vol. 17, 291-292, or according to applications US 2,876,071, DE 111 34 46, CS 263599 or GB 1,193,040.

Polysulfan (H2Sx, where x> 2), as impurities may be contained in the raw gas flow containing H2S. They are formed, for example within a certain temperature range, by cooling a flow of hot crude gas containing H2S, which is conducted from a reactor, where the H2S synthesis takes place. Above 350 ° C, H2Sx is unstable and decomposes into sulfur and H2S. In the temperature range of approximately 200 to 290 ° C, H2S reacts in the flow of crude gas with S, forming H2Sx. In the case of temperatures below 170 ° C, the formation of H2Sx does not fulfill any fundamental role.

The polysulfanes contained in the flow of raw gas containing H2S must not precipitate upon cooling in the facility used to produce H2S and must not decompose into sulfur and H2S after a certain residence time, since as a consequence sulfur depositions will occur. Therefore, the flow of crude gas containing H2S and the polysulfanes contained therein, in accordance with the invention, are conducted through catalytically active material contained in the container intended for it, for a controlled conversion of polysulfan into H2S and sulfur. Preferably, as catalytically active material active carbon and / or a molecular sieve and / or a hydrogenation catalyst are used, particularly preferably active carbon and / or a molecular sieve. As the hydrogenation catalyst, preferably a catalyst material containing at least one element selected from the group Ni, W, Mo, Co and V is used in an oxidic or sulfonic form, on an aluminum oxide or silicon oxide support. Especially preferably, the flow of crude gas containing H2S and the polysulfan all! contents are conducted through active carbon contained in a container and / or a molecular sieve, which are used as a catalyst for the controlled conversion of polysulfanes into H2S and sulfur. In the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, therefore, sulfur is produced from the transformation of the polysulphanes and eventually dragged sulfur droplets contained in the flow can be produced additionally. of raw gas, or an excess of sulfur provided for the synthesis. Preferably, however, the dragged sulfur droplets and an excess of sulfur are already separated in a refrigerant that is connected upstream of the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve.

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According to the invention, the flow of crude gas is conducted through the catalytically active material, preferably through the active carbon and / or the molecular sieve, at temperatures of 114 to 165 ° C, preferably 123 to 163 ° C, especially preferably from 127 to 162 ° C, in particular from 130 to 161 ° C, completely preferably from 135 to 160 ° C. These are the temperatures of the catalytically active material. Maintaining the temperature of the gas flow above 114 ° C during the passage through the active carbon and / or molecular sieve ensures that the sulfur that is produced (from the decomposition of H2Sx and eventually from the flow of crude gas) remain in the melt. By maintaining the temperature of the gas flow below 165 ° C, in particular below 160 ° C, the viscosity of sulfur saturated with H2S remains sufficiently reduced. Because of this, the sulfur that is present can flow from the catalytically active material, preferably from the active carbon (for example from an active carbon bed) and / or from the molecular sieve, and reach the bottom of the container containing the Catalytically active material, preferably active carbon and / or molecular sieve. The sulfur accumulated in the bottom, according to the invention, is redirected to produce H2S (preferably towards the reactor used for the synthesis of H2S).

Through the continuous discharge of sulfur from the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, the catalytically active material, preferably the active carbon and / or the molecular sieve, is not loaded with sulfur or it is barely loaded with sulfur. A change of the catalytically active material, preferably the active carbon and / or the molecular sieve, therefore, is not necessary or is only necessary rarely, so that a reduced consumption of catalytically active material is achieved, where the costs of elimination as well! such as damage to the environment, they can be largely avoided, for example in the case of carbon combustion. In addition, a second container with catalytically active material can be dispensed with, which should be changed in the case of a change of the catalytically active material in the first container. Through the reconduction of the sulfur that is produced in the vessel in the synthesis reaction it is possible to reduce the consumption of raw materials.

The invention further relates to a device for the continuous production of H2S hydrogen sulfide, which comprises a reactor for the reaction of sulfur and hydrogen, a refrigerant connected to the reactor, to cool a flow of crude gas containing H2S, from the reactor, at a temperature of 123 to 165 ° C, preferably 127 to 163 ° C, especially preferably 130 to 162 ° C, in particular 135 to 161 ° C, completely preferably 150 to 160 ° C , a container connected to the refrigerant, which contains catalytically active material, preferably active carbon and / or a molecular sieve, with a bottom for collecting sulfur that is present in the flow of crude gas containing polysulfan (H2Sx) from 114 to 165 ° C, preferably from 123 to 163 ° C, especially preferably from 127 to 162 ° C, in particular from 130 to 161 ° C, completely preferably from 135 to 160 ° C, and a line connected to the bottom of the container, which flows into the refrigerant, to redirect the sulfur to the reactor. The device according to the invention is used to execute the method according to the invention.

In the reactor the reaction for the H2S synthesis is carried out. A flow of crude gas containing H2S is conducted from the reactor to the refrigerant. The refrigerant cools that flow of crude gas from 114 to 165 ° C. From the refrigerant, a flow of crude gas containing H2S, which contains polysulphanes (H2Sx), is conducted into the container containing the catalytically active material, preferably active carbon and / or a molecular sieve. The sulfur present in the container at a temperature of 114 to 165 ° C, preferably 123 to 163 ° C, especially preferably 127 to 162 ° C, in particular 130 to 161 ° C, completely preferably from 135 to 160 ° C (coming from the decomposition of the polysulphanes, possibly from the separation of a surplus of sulfur and possibly from the separation of sulfur that was dragged, preferably from the decomposition of the polysulfan), it is collected in the bottom of the vessel and, indirectly by means of the refrigerant or, directly in the reactor, is redirected to the synthesis reaction. Preferably, the sulfur that is present is indirectly redirected to the reactor by the refrigerant. Separation of the droplets of entrained sulfur and excess sulfur takes place preferably in a refrigerant connected upstream of the container containing the catalytically active material (partial condenser).

According to a preferred embodiment of the present invention, the flow of crude gas is introduced into the container with an inlet temperature of 127 to 163 ° C, particularly preferably 130 to 162 ° C, in particular 135 at 161 ° C, completely preferably from 150 to 160 ° C, through the catalytically active material, preferably active carbon and / or a molecular sieve, and is conducted outside the container with an outlet temperature of 121 to 160 ° C, preferably from 124 to 158 ° C, especially preferably from 126 to 157 ° C, in particular from 130 to 156 ° C, completely preferably from 140 to 155 ° C. In this way, the flow of crude gas releases its heat, for example to a secondary circuit, which is heated for example at a temperature of 110 to 120 ° C, with which the refrigerant is operated.

The catalytically active material, preferably the active carbon and / or the molecular sieve, preferably flows from below (from the bottom) with the flow of crude gas, to ensure that the flow of purified crude gas leaving the upper part of the vessel does not contain no entrained sulfur that has been separated in the container. Preferably, the purification of the flow of crude gas containing polysulfan takes place in one step, in a

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only container that contains catalytically active material, preferably active carbon and / or a molecular sieve.

The catalytically active material, preferably the active carbon and / or the molecular sieve is present in the container preferably as a solid bed, with an apparent height of at least 1 m, preferably at least 1.5 m. The ratio of the height to the bed diameter is preferably 0.1 to 10, preferably 0.2 to 7, especially preferably 0.3 to 5, completely preferably 0.4 to 5, in particular from 0.5 to 2. Loss of pressure by means of the catalytically active material, preferably the active carbon bed and / or the molecular sieve bed, preferably complies with the condition

image 1

where f is between 0.05 and 0.5, preferably between 0.1 and 0.3, p represents the density of the raw gas flow, v represents the circulation speed of the raw gas flow in the inlet cross section of the container and Ap represents the loss of pressure by means of the catalytically active material.

As a material, any active carbon known to the expert, in particular active carbon produced from wood, coal, peat or coconut nut, can be used as a catalyst. Preferably, these are active carbon particles of a size of 2 to 15 mm, more preferably 3 to 5 mm. The active carbon can be present, for example, in the form of small cylinders with a diameter of 4 mm. The volume of the active carbon pores preferably amounts to more than 30 cm3 / 100 g. The inner surface of the active carbon is preferably> 900 m2 / g, especially preferably> 1100 m2 / g. The active carbon may comprise one or more kinds of active carbon. By way of example, a first layer of a first class of active carbon and a second layer disposed thereon of a second class of active carbon can be used in the active carbon container.

Suitable molecular sieves as catalytically active material are described for example in Robert H. Perry, and others, Chemical Engineers Handbook, McGraw-Hill Book Company, sixth edition. Molecular sieves of type 3A, type 4A, type 5A, type 10A, type 13X, silicalite, non-aluminized zeolite Y, mordenite and cabasite are preferred. A molecular sieve of type 4A is considered especially preferred.

Preferably, the flow of crude gas containing H2S is conducted through the container containing catalytically active material, preferably active carbon and / or molecular sieve, with a residence time in the empty tube of 1 to 200 s, preferably of 2 to 100 s, especially preferably 5 to 80 s, completely preferably 10 to 50 s. The speed of the empty tube is preferably 0.01 to 1 m / s, preferably 0.02 to 0.5 m / s, completely preferably 0.04 to 0.3 m / s, so completely preferred from 0.05 to 0.2 m / s. The absolute pressure in the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, preferably ranges from 0.2 to 20 bar, preferably from 0.4 to 10 bar, especially preferably from 0.8 to 6 bar, completely preferably 1 to 5 bar. A gas dispensing device, which contains bypass plates, inlet tubes and / or perforated inlet tubes, can be provided at the inlet of the container to distribute the flow of crude gas into the container.

According to a preferred embodiment of the present invention, the device according to the invention comprises a reactor for the continuous production of H2S through the conversion of a mixture of educts that essentially contains gaseous sulfur and hydrogen, into a catalyst, where the reactor comprises a sulfur melt in a lower part of the reactor, where gaseous hydrogen can be introduced through a delivery device. The catalyst (preferably as a solid bed) is arranged in at least one U-shaped tube, which is partially in contact with the sulfur melt, where at least one U-shaped tube has an opening on one side. inlet arranged above the sulfur melt, through which the mixture of educts can enter into the U-shaped tube, a flow path within at least one U-shaped tube, along which the mixture of educts can be converted into a reaction area, where the catalyst is arranged, and where at least one U-shaped tube has a passage opening on another side, through which a product towards a product area (separate from the educt area).

Preferably, the reactor comprises a cylindrical or prism-shaped central body, surrounded by a reactor cover, which at both ends is respectively closed by a bell. The bells can have any suitable shape, where for example they can be designed semi-spherically or conically.

Preferably, the reactor, in a lower part, is filled with a sulfur melt. Through a delivery device, gaseous hydrogen can be introduced into the sulfur melt, where above

From the sulfur melt a mixture of educts containing essentially gaseous sulfur and gaseous hydrogen accumulates in an area of educts, which, by means of a phase limit, is in contact with the sulfur melt, which is delimited upward preferably by a subdivision, for example by a base. In a preferred embodiment of the present invention, the base, in an upper part of the reactor, 5 is attached to the reactor cover, preferably in the upper third, especially preferably in the upper room of the internal space of the reactor .

In the reactor used, preferably at least one U-shaped tube is provided, which is in contact, at least partially, with the sulfur melt. Therefore, the reactor is designed as a multitubular reactor, with U-shaped contact tubes. A U-shaped tube of that class 10 has two sides which, at their lower ends, are connected to each other through of an arc-shaped area. The U-shaped tubes can have sides respectively of a different length or, preferably, of the same length. The U-shaped tubes may, for example, have a diameter of the sides between 2 and 20 cm, in particular between 2.5 and 15 cm, particularly preferably, between 5 and 8 cm. Preferably, at least one U-shaped tube is disposed vertically in the reactor, where the arc-shaped area is below and the two ends of the sides meet at the top.

In the context of the present invention, "being in contact" means that a heat exchange can take place between the sulfur melt and the internal space of the tube, by means of the tube wall. Preferably, at least one U-shaped tube is partially submerged in the sulfur melt.

Within at least one U-shaped tube a catalyst for hydrogen and sulfur conversion is preferably arranged to form H2S so that a reaction area is provided. At

In the context of the present invention, the area of reaction is called that area within the U-shaped tubes, where the catalyst is located. The conversion of the educts takes place mainly in the reaction area that contains the catalyst. Providing a reaction area in the U-shaped tubes allows a compact construction mode of the reactor in terms of the length of the reactor, since the reaction area 25 provided for the conversion of hydrogen with sulfur to form H2S can be divided into the two sides of a

U-shaped tube. Through the use of the catalyst, the conversion to form H2S can be performed at moderate temperatures and at a reduced pressure. Preferably, the catalyst is arranged in the form of a solid bed poured into at least one U-shaped tube. Catalysts containing, for example, cobalt and molybdenum on a support, which can be used as a base body, are considered suitable catalysts. anyway. By way of example, the diameter of the body rises from 2 to 12 mm, in particular it is between 3 and 10 mm, particularly preferably between 4 and 8 mm, and the length is preferably between 2 and 12 mm, in particular between 3 and 10 mm, especially preferably between 4 and 8 mm.

During the production of hydrogen sulfide using the preferred embodiment of the reactor, the mixture of educts enters from the area of educts to the side of at least one U-shaped tube, through at least one inlet opening. The inlet opening is arranged on one side of at least one U-shaped tube, above the sulfur melt. The inlet opening, from the educts area, flows into one side of the U-shaped tube. The distance between the phase limit of the sulfur melt and the inlet opening of the U-shaped tube is selected so that the least amount of little liquid sulfur is trapped in the form of drops with the flow of the mixture of educts, into the internal space of the U-shaped tubes. The distance between the inlet opening and the phase limit of the sulfur melt is preferably located between 0.3 and 3 m, in

in particular between 0.6 and 2.5 m, particularly preferably between 0.9 and 2 m.

In the production of hydrogen sulphide using the preferred embodiment of the reactor, the mixture of educts passes through the U-shaped tube along a flow path, that is, first, after entering through the opening of Inlet, it crosses one side of the U-shaped tube, from top to bottom, crosses the arc-shaped area of the U-shaped tube to the second side, finally crossing the second side from the bottom up. The mixture of educts reacts mainly in the reaction area that is contained within the U-shaped tube, in the catalyst disposed therein. Through an outlet opening on the second side of the U-shaped tube, the gas containing the product enters a product area (preferably arranged above the sulfur melt and above the educt area), which is 50 separated from the area of educts (for example through a base).

The reactor is supplied with hydrogen gas and liquid sulfur, preferably by means of a suitable delivery device. In a suitable place, from the product area of the reactor, the hydrogen sulfide product is conducted, for example in an upper hood.

The two sides of a U-shaped tube, preferably respectively at an upper end, are attached to a base of the reactor, which in turn is suitably fixed to an upper part of the reactor, on the cover. of the reactor. Preferably, the reactor base subdivides the reactor into two parts, in particular determining an area of products located above. The preferential fixation of at least one U-shaped tube in a base attached to the reactor cover allows thermal modifications of the length of the reactor and of the tubes in

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U-shaped, independently of each other, since the U-shaped tubular beam is only fixed by means of the base in the reactor cover, so that in the construction of the reactor compensators can be dispensed with. Through the union of the U-shaped tubes with the base at the upper ends of their sides, advantageously, the tubes are stabilized in correspondence with the force of gravity.

In accordance with a preferred embodiment of the present invention, in a top section of the reactor, preferably near the upper hood, a base is arranged that divides the internal space of the reactor into a lower part located below and an upper part located above.

Preferably, the upper part contains the product area, which during the operation of the reactor mainly contains the hydrogen sulfide product. Respectively one side of the U-shaped tubes is in an open connection with the product area.

The lower part of the reactor preferably contains the educt area directly below the base and below a sulfur melt, where liquid sulfur is supplied from an external source and / or as a return. The U-shaped tubes are partially in thermal contact with the sulfur melt, where they are preferably partially arranged directly in the sulfur melt, thus immersing themselves in the sulfur melt. In this way a transmission of the thermal energy takes place that is released in the exothermic reaction to form H2S, by means of at least a U-shaped tube, towards the surrounding sulfur melt. The heat of reaction is used for an evaporation of the sulfur contained within. This thermal coupling enables a convenient process from the energy point of view, where the external heat supply is reduced considerably or is not necessary. At the same time, overheating of the catalyst can be avoided, thanks to which the useful life of the catalyst is increased.

For a good transmission of thermal energy, preferably, the thermal resistance of the catalyst charge is kept as low as possible in the reaction area. Preferably, a plurality of U-shaped tubes containing the catalyst are provided for the conversion of the educts to form H2S, so that the respective route from the center of the catalyst charge to the tube wall is reduced. Preferably, the ratio of the sum of the cross-sectional surfaces of all the contact tubes (as well as all the sides of the U-shaped contact tubes), referred to the surface of the cross section of the body of the reactor (preferably cylindrical), is located between 0.05 and 0.9; in particular between 0.15 and 0.7; especially preferably between 0.2 and 0.5; completely preferably between 0.25 and 0.4.

In order for there to be sufficient thermal contact for heat transmission from the U-shaped tube to the surrounding sulfur melt, it is intended that 20 to 100% of the external lateral surface of a U-shaped tube respectively be found in contact with the sulfur melt along the reaction area that contains the catalyst. For the heat transmission to the sulfur melt to work properly, at the place where the reaction takes place in the U-shaped tube, the outer lateral surface of the U-shaped tube, along the reaction area containing the catalyst, it must be surrounded by the sulfur melt in more than 20%, preferably in more than 50%, especially preferably in more than 80%. In the case of a too low load level of the sulfur melt in the reactor and, thus, a too small contact of the U-shaped tube and the sulfur melt, there is a danger that the heat of reaction does not dissipate sufficiently.

In the flow direction of the mixture of educts, within at least one U-shaped tube, the mixture of educts, after entering the U-shaped tube, can first pass through an inert bed, where sulfur eventually trapped , contained in the form of drops, separates in that inert bed from the mixture of educts. By way of example, a part of the liquid sulfur may be present in the mixture of educts containing hydrogen gas and sulfur, up to 100,000 by weight in parts per million. For the separation of the sulfur droplets, preferably, a part of the inert bed, referred to the total bed based on the inert bed and the catalyst bed, is provided in at least one U-shaped tube, from 1 to 30 %, in particular from 2 to 25%, preferably from 5 to 20%, particularly preferably from 8 to 16%. The inert bed can be composed of bodies of any shape, for example by stacking or preferably by spheres, which are of a suitable material, for example of zirconium oxide or preferably of aluminum oxide.

Preferably, gaseous hydrogen is conducted to the sulfur melt in the reactor by means of a delivery device, distributed in the sulfur melt by a distributor device.

Preferably, the distributor device comprises a distributor plate arranged horizontally in the reactor and an edge extending downward. The hydrogen introduced below the distributor device accumulates under the distributor plate forming a hydrogen bubble in the space bounded by the edge that extends downwards and the distributor plate.

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Preferably, the delivery device comprises an open tube at both ends, arranged vertically in the reactor, which is disposed below the distributor device and whose upper end preferably protrudes inward, in the space limited by the plate of the distributor and along the edge that extends downward, where it preferably protrudes into the hydrogen bubble. By protruding inwards in the space below the distributor plate and especially in the hydrogen bubble formed below, advantageously, an irregular hydrogen inlet into the sulfur melt is prevented.

In the vertical tube of the supply device, preferably laterally, an inlet pipe extends obliquely, through which hydrogen is introduced from outside the reactor. Advantageously, the supply device is designed so that the sulfur entering the tube arranged vertically can be freely discharged downwards, without obstructing the hydrogen supply device. The hydrogen rises upwards in the tube arranged vertically, accumulating below the distributor device.

Preferably, the distributor device comprises a distributor plate arranged horizontally in the reactor (preferably with passage openings), and an edge extending downward. The preferably flat distributor plate extends over almost the entire surface of the reactor cross section, where an opening remains between the reactor cover and the distributor device. The opening between the edge of the distributor device and the reactor cover preferably has a width of between 1 and 50 mm, in particular between 2 and 25 mm, particularly preferably between 5 and 10 mm. The shape of the distributor plate is oriented according to the geometry of the reactor, where it is arranged. It can be, for example, circular or polyiangular, or it can have any other shape. Preferably, in the outer circumference of the distributor plate, recesses can be provided which constitute passage openings for example for a hydrogen line, a sulfur inlet line and a sulfur reconduction line. Thus, the opening between the distributor device and the reactor cover can only have a reduced width, so that an oscillation of the distributor device in the reactor is avoided. The hydrogen introduced below the distributor device accumulates under that distributor plate forming a hydrogen bubble in the space bounded by the edge that extends downwards and the distributor plate. Preferably, the distributor plate is arranged horizontally in the reactor, so that the hydrogen bubble that accumulates below the distributor plate has an almost constant height.

The accumulated hydrogen, by the edge that extends downwards when the hydrogen bubble has reached a certain height, and / or through the passage openings provided in the distributor plate, is distributed in the sulfur melt. Hydrogen from the hydrogen bubble, through the edge, through a space between the distributor device and the reactor cover, can be distributed in the sulfur melt. Preferably, the edge area of the dispensing device is designed as a tip, whereby the accumulated hydrogen can be distributed in fine gas bubbles.

In a preferred embodiment, the distributor plate, of the distributor device, preferably arranged horizontally in the reactor, contains passage openings. Through the passage openings in the distributor plate, the accumulated hydrogen is dispersed distributed regularly from the hydrogen bubble to the sulfur melt that is located on the distributor plate. The amount of the passage openings in the distributor plate, among other things, is oriented to the volumetric flow of the introduced hydrogen and preferably amounts from 2 to 100, in particular from 4 to 50, especially preferably from 8 to 20 per 100 Norm-m3 / h. The passage openings can be made, for example, circularly or as grooves, where the preferred diameters, as well! as the widths of the groove, they are located from 2 to 30 mm, preferably from 5 to 20 mm, especially preferably from 7 to 15 mm. Preferably, the passage openings are arranged regularly on the distributor plate. The part of the surface of the passage openings, referred to the surface of the distributor plate, is preferably between 0.001 and 5%, preferably between 0.02 and 1%, especially preferably between 0.08 and 0, 5 %.

To achieve a good mixing of the sulfur melt through the ascending hydrogen and, thereby, to ensure as efficient as possible trapping of the sulfur in the ascending hydrogen, the gas velocity, of the hydrogen dispersed through the openings in passing, it is preferably located between 20 and 500 m / s, in particular between 50 and 350 m / s, preferably between 90 and 350 m / s, especially preferably between 150 and 250 m / s.

If, in particular, in the event of a temperature drop, sulfur enters the passage openings, which solidifies in the passage openings, the hydrogen distribution stops at the dispensing device through the passage openings. . The accumulated hydrogen can also be dispersed over the area of the edge that extends downwards, towards the sulfur melt, where the hydrogen is then distributed from the hydrogen bubble, into the sulfur melt contained in an opening between the distributor device and the reactor cover. Preferably, the edge area of the dispensing device is designed as a tip, whereby the hydrogen accumulated below is distributed in fine gas bubbles.

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In the case of a simple introduction of hydrogen into the sulfur melt, for example by means of a vertical introduction tube without such a dispensing device, a non-homogeneous distribution of the hydrogen can result. In the vicinity of the introduction tube, large hydrogen bubbles rise to the sulfur melt. In other areas of the sulfur melt, hydrogen is barely present. Due to this, oscillations of the U-shaped tube can occur. In the preferred embodiment of the reactor, the distributor device contained in the reactor according to the invention, made as a bell open downwards, thus also serves to stabilize the tubes U-shaped tubular beam.

To achieve greater stability of the U-shaped tubes, at least one U-shaped tube can be connected to the distributor device near its lower arc-shaped area, which, through its sizing, limits the range of oscillations of the U-shaped tube, ace! as of the corresponding tubular beam, in horizontal direction. In this way, the distributor device, in turn, is not directly connected to the reactor cover, but rather is indirectly connected to the reactor cover, by joining the U-shaped tubes with base. Thanks to this, problems can be avoided due to tensions between the reactor, the U-shaped tubes and the distributor device, caused by thermal changes in length.

In one embodiment, the distributor plate is connected to the respective sides of at least one U-shaped tube, near the lower end of the U-shaped tube, for example by welding, where a section of the tube in the form of U, which comprises at least a part of the arc-shaped area, is located below the distributor plate. Since that section of the U-shaped tube is not in contact with the sulfur melt, but rather protrudes in the area of the hydrogen bubble accumulated below the distributor device, the U-shaped tube preferably in that section does not contain a catalyst bed. In this way there is no conversion to form H2S and there is no heat of exothermic reaction that must be dissipated. Within at least one U-shaped tube, subdivisions can be provided that separate the catalyst bed area from the bedless area, where the subdivisions must however be permeable for educts and products of H2S production.

Preferably, in the present invention there is provided a delivery device and a distributor device for hydrogen gas in a lower section of the reactor, for example near the bottom bell. The hydrogen introduced by the supply device towards the sulfur melt rises through the melt in the form of gas bubbles distributed through the distributor device, due to which sulfur is trapped from the melt, accumulating in the area of reactor educts (for example below an upper reactor base), as a mixture of educts that is in contact with the sulfur melt by a phase limit.

The mixture of educts contains gaseous hydrogen and sulfur in a molar ratio that is regulated through the dominant parameters in the process, that is, temperature, pressure and the amount of hydrogen introduced, corresponding to the sulfur evaporation equilibrium. Thus, through the selection of the process parameters, an excess of hydrogen or sulfur or a molar ratio corresponding to the stoichiometry of the reaction can be regulated, depending on the desired reaction reaction condition to form H2S. Preferably, in the case of the present invention, an excess of sulfur is regulated, in order to achieve as complete a conversion as possible of the hydrogen with the sulfur, to form H2S. Preferably, the excess sulfur per kilogram of H2S generated is between 0.2 and 3.0; in particular between 0.4 and 2.2; preferably between 0.6 and 1.6; especially preferably between 0.9 and 1.2.

The method for the continuous production of H2S preferably comprises the conversion of a mixture of educts that essentially contains gaseous sulfur and hydrogen, into a catalyst, where a sulfur melt is preferably provided at least in a lower part of the reactor, where introduces gaseous hydrogen. During the method, the mixture of educts, for example from an area of educts, can be led to the side of at least one U-shaped tube, through at least one inlet opening arranged above the melt of sulfur, along a flow path, through at least one U-shaped tube that is partially in contact with the sulfur melt, and can be converted into a catalyst arranged in the flow path, in a reaction area. A product can be conducted from at least one outlet opening to another side of the U-shaped tube, to a product area (preferably separated from the educt area). Preferably, the H2S synthesis is performed in the reactor described above.

The preferred method for the synthesis of H2S is carried out in the reactor at temperatures of the mixture of educts and the reaction area containing the catalyst from 300 to 450 ° C, preferably from 320 to 425 ° C, especially preferably from 330 at 400 ° C, due to which the corrosion load of the selected materials, of the construction elements, remains reduced. Preferably, the sulfur melt temperature is between 300 and 450 ° C, in particular between 320 and 425 ° C, preferably between 330 and 400 ° C, especially preferably between 350 and 360 ° C. The temperature in the educt space on the sulfur bath is preferably between 300 and 450 ° C, in particular between 320 and 425 ° C, preferably between 330 and 400 ° C, especially preferably between 350 and 360 ° C. The mixture of products that leaves from the reaction area to the product space preferably has a temperature of between 300 and 450 ° C, in particular between 320

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and 425 ° C, preferably between 330 and 400 ° C, especially preferably between 350 and 360 ° C. The absolute pressures in the reactor cover space and inside the U-shaped tubes are preferably between 0.5 to 10 bar, in particular between 0.75 and 5 bar, preferably between 1 and 3 bar and especially preferably between 1.1 and 1.4 bar.

Preferably, the hydrogen introduced into the reactor in the preferred method is dispersed in a distributor device provided in the lower section of the reactor, in the sulfur melt. First, the distribution of the hydrogen in the mass of molten sulfur contained in the distributor plate preferably takes place by means of a distributor plate, of the distributor device, arranged horizontally in the reactor, through the passage openings provided therefor and / or by the area of the edge, of the edge that extends downwards, of the dispensing device, coming from a hydrogen bubble accumulated below. For example, if the hydrogen passage is stopped through the passage openings, for example due to sulfur deposited inside, the hydrogen bubble accumulates in the space delimited by the distributor plate and the edge of the dispensing device that extends downwards, so that, secondly, hydrogen is distributed over the area of the edge that extends downwards, towards the sulfur melt that surrounds it. In this way, the hydrogen, from the hydrogen bubble, arrives below the distributor device, through an opening between the distributor device and the reactor cover, reaching the sulfur melt present on the distributor device. This ensures that the hydrogen is distributed in the sulfur melt in sufficient quantity during the continuous production of H2S.

The evaporation rate of sulfur, in the present invention, is preferably regulated so that the mixture of educts contains an excess of sulfur. The excess sulfur is derived with the product from the product area of the reactor and subsequently separated as a melt. That liquid sulfur can be redirected to the sulfur melt contained in the bottom of the reactor, for example by a collection and derivation construction arranged in the top of the reactor, which, among other things, comprises a collection bottom and a return tube submerged in the sulfur melt, which starts from said bottom. Preferably, a cooling of the H2S gases leaving the reactor takes place in a heat exchanger that serves as a refrigerant, where the excess sulfur is condensed and conducted back to the sulfur melt through the collection and collection construction. derivation. As a cooling medium, hot pressurized water can be introduced into a secondary circuit.

According to a preferred form of the method according to the invention, it comprises the steps

• reaction of sulfur gas and hydrogen in a catalyst (preferably solid), in a reactor, with a

excess sulfur, to obtain a flow of crude gas containing H2S,

• cooling the flow of crude gas at a temperature between 123 and 165 ° C, preferably between 127 and 163

° C, especially preferably between 130 and 162 ° C, in particular between 135 and 161 ° C, so

completely preferred between 150 and 160 ° C, in a refrigerant to separate excess sulfur, and

• conduction of the flow of raw gas from the refrigerant to the container containing the material

catalytically active, preferably active carbon and / or molecular sieve.

The flow of crude gas containing H2S, conducted from the reactor, preferably has a temperature of 290 to 400 ° C. The excess sulfur is condensed at least partially in the refrigerant As a cooling medium, for example, hot water can be used at 120 ° C, in a secondary circuit. The sulfur that is present in the refrigerant is redirected to the reactor to produce H2S. In this way, the sulfur can be redirected to the sulfur melt in the area of the reactor shell, by means of a special collection and diversion construction.

According to the method according to the invention a line is provided between the refrigerant and the reactor, through which the flow of crude gas is conducted in a direction from the reactor to the refrigerant, and through the reconducted sulfur it is conducted in a opposite direction, from the refrigerant to the reactor. The sulfur condensed in the refrigerant from the flow of crude gas containing H2, by way of example, can return at the bottom of the same tube to the reactor, through which the flow of raw gas containing H2S is conducted from the product area of the reactor towards the refrigerant. Thanks to this, an additional return duct can be avoided. Among other things, this simplified tube pipe has the advantage that two flanges can be saved that represent possible leakage points, from which the highly toxic hydrogen sulfide could escape. Another advantage lies in the fact that the common line acts as a countercurrent heat exchanger, where the returning sulfur cools the hydrogen sulfide. In this way, the refrigerant can be developed for a lower cooling capacity. The sulfur that returns cools the hydrogen sulfide directly after entering the reactor product area, so that the production area is protected against areas of gas that are too hot and, with it, corrosion.

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It is striking that, for example, sulfur that leaves the reactor with 350 ° C, which is already less viscous and, for example, sulfur that returns with 120 ° C, which is still very viscous, can be conducted in a reverse flow, without the sulfur with high viscosity, with 200 ° C, block the union tube. It is known that the sulfur that comes from the reactor with H2S is saturated and that H2S reduces the viscosity of the sulfur by approximately around the 100 factor, where however that cannot be considered sufficient.

According to a preferred embodiment of the present invention, the sulfur collected at the bottom of the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, is redirected to the reactor by means of the refrigerant. Preferably, there is provided a line between the refrigerant and the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, through which the flow of crude gas is conducted in a direction from the refrigerant towards the container, and through the sulfur collected at the bottom of the container it is conducted in an opposite direction, from the container to the refrigerant. The sulfur that forms in the container, for example during the decomposition of H2SX, flows from the catalytically active material, preferably the active carbon (for example from a bed of active carbon) and / or the molecular sieve, accumulating at the bottom of the container. The temperatures in the container are selected so that the sulfur is in the liquid state and, therefore, can circulate in the bottom and, from there, can reach the refrigerant through the line. Through the arrangement of a single line between the container containing the catalytically active material, preferably the active carbon and / or the molecular sieve, and the refrigerant to drive the flow of cooled crude gas in a direction from the refrigerant to the container and to redirect sulfur in the opposite direction, from the bottom of the container to the coolant, in turn is saved in flanges that can represent possible leakage points. The interconnection of tubular lines is simplified.

Preferably, the lines of the device that conduct the liquid or gaseous sulfur, in particular the line between the container containing the active carbon and / or the molecular sieve and the refrigerant, between the reactor and the refrigerant and / or the inlet line of reactor sulfur, are designed with slope. In addition, preferably, these lines are made with a temperature regulation of 100 to 170 ° C. For this, the use of double-covered lines or the coating of the lines with temperature-controlled corrugated flexible tubes, or an electric heating, is considered adequate. Preferably, lines with double cover or corrugated hoses are used. As temperature regulating means in the double cover or in the corrugated flexible tube, for example, water vapor or liquid water under increased pressure is considered suitable.

Next, the invention is explained in detail by drawing.

The drawing shows:

Figure 1: a schematic representation of a preferred embodiment of a device according

With the invention.

The device according to figure 1 is suitable for executing the method according to the invention. Said device comprises a reactor 1 to convert sulfur and hydrogen, a refrigerant 40 connected to reactor 1 to cool a flow of crude gas containing H2S, conducted from reactor 1, at a temperature of 114 to 165 ° C, and a container 42 containing active carbon 41, connected to the refrigerant 40, with a bottom 43 for collecting sulfur that is produced in the container 42 at a temperature of 114 to 165 ° C, from the flow of crude gas containing polysulfan. A line 44 is connected to the bottom 43 of the container 42, which flows into the refrigerant 40, to redirect sulfur (through the refrigerant 40) to the reactor 1.

The reactor 1 is closed on both sides of a cylindrical body 2, with bells 3, 4. A product can be extracted in the upper bell 3. In the lower bell 4 there is a discharge connection 5 to eventually completely discharge the contents of the reactor 1. In a higher section of the reactor 1 there is provided a base 6 that separates an upper part with a product area 7 from a lower part 8. The base 6 is connected to a reactor cover 25 of the reactor 1. The lower part 8 is partially filled with a sulfur melt 9 which is in contact with an area of educts 10 by means of a phase limit, which It is bounded up by the base 6. The area of educts 10 contains mainly hydrogen gas and sulfur.

The hydrogen is conducted by a supply device 11 towards a lower section of the reactor 1, for example in the lower hood 4, towards the sulfur melt. The delivery device 11 comprises a line 12 that extends obliquely, which flows laterally into a tube 13 open up and down, arranged vertically in the reactor 1. The upper end of the tube 13 protrudes into a space 14 that is delimited by a distributor device 15. The distributor device 15 comprises a distributor plate 16 arranged horizontally in the reactor 1 and an edge 17 extending downward, which preferably has an area of the edge 18 made in the form on end. The hydrogen introduced by the delivery device 11 rises in the vertical tube 13, upwards, accumulating below the distributor plate 16, forming a hydrogen bubble. Through passage openings 19 in the distributor plate 16, the hydrogen is dispersed in the sulfur melt 9 above, rising into the mass

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sulfur molten 9 in the form of gas bubbles, upwards, where sulfur is trapped from the sulfur melt 9. Because of this, above the sulfur molten mass 9, in the area of educts 10, a mixture of educts that contains gaseous hydrogen and sulfur.

If the passage openings 19 in the distributor plate 16 are blocked for the passage of hydrogen, then the hydrogen, also from the hydrogen bubble accumulated below the distributor plate 16, through the area of the edge 18, can be dispersed towards an opening 20 between the reactor cover 25 and the edge 17 of the distributor device 15, towards the sulfur melt 9.

Tubes 21 are arranged in the cylindrical body of the reactor 1 which are designed in a U-shape. The U-shaped tubes 21 are connected to the base 6 on their two sides 26, 27. The union of the sides 26, 27 with the Base 6 can be produced through a welding seam. The U-shaped tubes 21 are partially submerged in the sulfur melt 9, due to which the possibility of direct heat exchange between the internal space of the tubes 21 and the sulfur melt 9 is provided, by means of the external lateral surface 28 of the tubes 21. Within each U-shaped tube 21 a solid bed of the catalyst 22 is provided, which is provided on both sides 26, 27 of the U-shaped tubes 21.

As shown in Figure 1, the distributor device 15 is connected to the U-shaped tubes 21, where a part and in particular the passage from one side 26 to a second side 27 of the respective U-shaped tubes 21 extends below the distributor plate 16, through space 14. Since that section of the U-shaped tubes 21 protrudes in the accumulated hydrogen bubble and is not in direct contact with the sulfur melt 9 , that section does not contain a catalyst. The opening 20 is positioned between the distributor device 15 and the reactor cover 25 The distributor device 15 is not directly connected to the reactor cover 25.

In reactor 1, hydrogen sulfide synthesis occurs as follows. A mixture of educts exits from the educt area 10 through one or more inlet openings 23 arranged in the circumference of one side 26 of each of the U-shaped tubes 21, towards the inner space of one side 26 of the U-shaped tube 21, it passes through the bed of the catalyst 22 contained therein, which may be complemented by an inert bed located upstream and, along the flow path, is converted to a large extent by forming sulfide of hydrogen in the reaction area contained in the solid bed of the catalyst 22. The product, on the second side 27, exits into the product area 7 through at least one passage opening 24 and can be collected and conducted from there! by means of the bell 3. Through the direct contact of the U-shaped tubes 21 with the sulfur melt 9, the reaction heat that is released during the conversion to form H2S is dissipated from the solid bed of the catalyst 22 towards the sulfur melt 9 by the outer lateral surface 28 of the U-shaped tubes, along the reaction area, and is used for a sulfur evaporation.

To maintain the sulfur melt 9 at approximately the same level during the process, gaseous hydrogen and liquid sulfur are supplied in amounts corresponding to the reactor continuously, by means of the delivery device 11 and a sulfur inlet line 29.

Between the reactor 1 and the refrigerant 40, a first line 30 is arranged which serves to drive the flow of crude gas from the reactor 1 to the refrigerant 40 and to redirect sulfur in the opposite direction, from the refrigerant 40 to the reactor 1. From the first line 30, the liquid sulfur reaches a construction of

collection and diversion 45 arranged in an upper part of the reactor 1. Said construction of collection and

branch 45 comprises a collection base 31, where input connections 34 are arranged to drive the product from the product area 7 which is below the collection base 31, to the product area 7 above , and an edge 35. The separated liquid sulfur is collected on a collection base 31 that is arranged horizontally in the product area 7 of the reactor 1, and is redirected to the sulfur melt 9 contained in the lower part of the reactor 8, by means of a return tube 32 immersed in the sulfur melt 9. Preferably, the reactor 1 is isolated, so that the energy consumption is as low as possible.

In the refrigerant 40, the flow of raw gas containing H2S, from the reactor 1, of approximately 350 ° C is cooled to 114 to 165 ° C. Thus, the excess sulfur that is redirected to the reactor 1 is condensed. through the first line 30. In the refrigerant 40 conditions are present under which polysulfan (H2Sx) can be formed. From the refrigerant 40, a flow of raw gas containing H2S, which contains polysulfan, is conducted through the second line 44, to the container 42 containing carbon

active 41. The second line 44 disposed between the container 42 containing the active carbon 41 and the refrigerant 40

it serves both to drive the flow of cooled crude gas towards one direction, from the refrigerant 40 to the container 42, as well as to redirect sulfur in the opposite direction, from the bottom 43 of the container 42 towards the refrigerant 40.

The flow containing H2S, purified by active carbon 41, is derived from the container 42 by an additional line 33.

In a preferred alternative embodiment, a molecular sieve is used as a catalytically active material instead of the active carbon 41.

Reference List

 1 reactor

 40 refrigerant

 2 reactor body

 41 active carbon

 3 top bell

 42 bowl

 4 bottom bell

 43 background

 5 download connection

 44 second line

 6 base 7 product area 8 bottom of the reactor 9 sulfur melt 10 educt area 11 hydrogen supply device 12 line 13 tube arranged vertically 14 space 15 distributor device 16 distributor plate 17 edge 18 edge area 19 passage openings 20 opening 21 tubes 22 solid catalyst bed 23 inlet opening 24 outlet opening 25 reactor cover 26 first side 27 second side

 43 collection and derivation construction

28 outer side surface

29 sulfur inlet duct

30 first line

31 collection base

32 return tube

33 line

34 input connections

35 edge

Claims (9)

5 10 fifteen twenty 25 30 35 40 Four. Five 1. Method for the continuous production of H2S hydrogen sulfide, where polysulfan (H2SX) content is found in a flow of raw gas containing H2S that occurs during production, characterized in that the flow of crude gas is conducted at temperatures of 114 at 165 ° through catalytically active material (41) that is contained in a container (42), and the sulfur that accumulates at the bottom (43) of the container (42) is collected and redirected to produce H2S, where a line (30) is arranged between a refrigerant (40) and the reactor (1), through which the flow of crude gas is conducted in a direction from the reactor (1) to the refrigerant (40) and is conducted in an opposite direction, from the refrigerant (40) to the reactor (1), through the redirected sulfur. 2. Method according to claim 1, characterized in that the flow of crude gas is introduced into the vessel (42) with an inlet temperature of 123 to 165 ° C, is conducted through catalytically active material in the form of active carbon (41 ) and is driven out of the container (42) with an outlet temperature of 121 to 160 ° C. 3. Method according to claim 1, characterized in that the flow of crude gas is introduced into the vessel (42) with an inlet temperature of 123 to 165 ° C, is conducted through catalytically active material in the form of a molecular sieve and It is driven out of the container (42) with an outlet temperature of 121 to 160 ° C. 4. Method according to one of claims 1 to 3, which comprises the steps • reaction of sulfur gas and hydrogen in a catalyst (22), in a reactor (1), with an excess of sulfur, to obtain a flow of crude gas containing H2S, • cooling the flow of crude gas from 114 to 165 ° C in a refrigerant (40) to separate excess sulfur and • conduction of the flow of crude gas from the refrigerant (40) to the container (42) containing the catalytically active material (41). 5. Method according to claim 4, characterized in that the sulfur that is present in the refrigerant (40) is redirected to the reactor (1) to produce H2S. 6. Method according to claim 4 or 5, characterized in that the sulfur collected in the bottom (43) of the container (42) containing the catalytically active material (41) is redirected to the reactor (1) by means of the refrigerant (40). 7. Method according to claim 6, characterized in that a line (44) is provided between the refrigerant (40) and the container (42) containing the catalytically active material (41), through which the flow of crude gas is conducted in a direction from the refrigerant (40) to the container (42) and, through the sulfur collected at the bottom (43) of the container (42), is conducted in an opposite direction, from the container (42) to the refrigerant (40). 8. Device for the continuous production of hydrogen sulfide H2S, which comprises a reactor (1) for reacting sulfur and hydrogen, a refrigerant (40) connected to the reactor (1) to cool a flow of 114 to 165 ° C raw gas containing H2S, coming from the reactor (1), a container (42) containing catalytically active material (41), connected to the refrigerant (40), with a bottom (43) to collect sulfur obtained from the gas flow crude which comprises polysulfan (H2Sx) in the container (42) from 114 to 165 ° C, and a line (44) connected to the bottom (43) of the container (42), which flows into the refrigerant (40) or into the reactor (1), to redirect sulfur, characterized in that a first line (30) is arranged between the reactor (1) and the refrigerant (40) to conduct the flow of crude gas in a direction from the reactor (1) to the refrigerant (40) and to redirect the sulfur in an opposite direction, from the refrigerant (40) to the r eactor (1). Device according to claim 8, characterized in that a second line (44) is provided between the refrigerant (40) and the container (42) containing the catalytically active material (41) to drive the flow of cooled crude gas in one direction from the refrigerant (40) to the container (42) and to redirect sulfur in an opposite direction, from the bottom (43) of the container (42) to the refrigerant (40).